Process of bleaching, dyeing, and printing vegetable and animal fiber material, fabrics, or felt



l Patented Oct. 11, 1932 UNITED STATES PATENT orrlca KURT LINDNER, F ORANIENBURG, NEAR BERLIN, GERMANY, ASSIGNOR T0 CHEE- ISGHE FABRIK MILCH AKTIEN-GESELLSCHAFT, OF BERLIN, GERMANY PROCESS OF BLEAGHING, DYEING, AND PRINTING VEGETABLE AND ANIMAL FIBER MATERIAL, FABRICS, 0R FELT No Drawing. Application filed January 14, 1926, Serial No. 81,311, and in Germany January 14, 1925.

der atmospheric pressure. Only after such.

preparatory treatment can the fiber be wet: ted,

the heretofore common method of using solutions of bleaching media such as chloride of lime, sodium hypochlorite, hydrogen peroxi'de, potassium permanganate, etc.

Various efforts have been made to avoid the said preliminary boiling process, and to subject the fiber material exclusively to cold bleaching. For example, it-has been proosed to moisten cotton in vacuo by cold al- 26 iiali solutions and to bleach the same after such treatment. Further, it has been tried to wet the fiber material in vacuo by means of concentrated solutions of chlorin.

Other efforts to facilitate wetting and permeating of the vegetable fiber by means of bleaching agents consist in adding wetting agents to the said agents such for example as soap, Turkey-red 011, glycerin, alcohol, and the like. By adding exclusively alcoholic matter to the bleaching mediumv satisfactory bleaching is not possible, and when adding soap or Turkey-red oils to the bleaching medium, bleaching is interfered with by the formation of lime soap, so that bleaching is unsatisfactory and non-uniform. Addmg such wetting agents to solutions of chloride of-lime is highly impractical because of the rapid formation-of l1me soap which renders such wetting agents ineffective and of course interferes with the bleaching process.

Similar difficulties are met with in the art of dyeing, where likewisecertain media have been added to the dye-stuffs for imroving the dissolving or rubbin of the dyestufis, wetting and permeating t e fiber mapermeated and thoroughly bleached by terial, more uniformly applying the dyestufli's and causing increased absorption of the dye-stuffs by the fiber material and a more effective utilization of the dyeing baths. Such additions are for example ethyl alcohol, hetero-cyclic bases, particularl pyridin', albumin and the derivatives thereo Turkeyred oil, monopol-soap and ordinary soap. Monopol-soap is a name sometimes applied to the sodium salt of ricinoleic acid. These additions are objectionable for various reasons, the additions having a low efliciency and being uneconomical. For example, most of thesaid ingredients are not appropriate for dyeing wool in acetic or sulphuric acid baths, because in caseof organic bases, inactive salts are formed, and in case of soaps, Turkey-red oils, and the like, decompositions take place with the production of fatty acids which are insoluble in water. Also in case of oils which are stable in acids the dispersing property is reduced, so that the favorable action is largely lost.

I have discovered that many aromatic sulphonic acids substituted by aliphatic radicals, and their alkali metal, alkaline earth metal and metal salts are very effective wetting agents, which are not impaired in the presence of bleaching media such as chloride of lime, etc., because of the formation of insoluble calcium salts. The following substances have proved very effective: palmitobenzol-sulphonic-acid, stearo toluol sulphoni c a c id, isopropyl-naphthalene-sulphonicacid, isobutyl-naphthalene-suphonic-acid, cyclo-hexyl-naphthalene-sulphonic-acid, a n d the salts of the said compounds. All of the said acids, and also the alkali metal, alkali earth metal and metal salts thereof, are soluble in water. Therefore, as distinguished from the wetting agents heretofore proposed, they are perfectly stable as against acids, salts, and calcium compounds of any kind. For example, in the manufacture of dyeing baths, the solutions of the said compounds are suitable for forming the dye-stuff into a paste, and they improve the dispersion of the dye-stuff, and thereby they prevent too rapid. and non-uniform absorption of the dye-stuff they improve the tints and the rubbing property, and they prevent the formation of bronze. The property of improving the suspension and emulsion is particularly important when dyeing matter containing oily impurities, which by reason of the said impurities are not easily uniformly dyed. For example, oily cotton obtained as a waste roduct from spinning mills and weaving actories, or carpet yarns containing residues of oils which cannot be saponified can be uniformly dyed without having the residue of the fat removed.

Even slight additions, such as from 0.01 to 1.0%, of the said ingredients added to the bleaching lye or the dyers bath are sufiicient to insure good bleaching and dyeing, the result being similar to the one obtained when subjecting the fiber material to the aforesaid preliminary boiling process. The fiber material is moistened almost instantaneously, audit is thoroughly bleached within a short period of time. The process is suitable for treating fiber material in open vats and in other apparatus. Further, it is suitable for treating loose fiber material, skeins and fabrics.

In bleaching, my improved process is important for the reason that the ingredients can be added to bleaching media of any kind, and particularly to the chloride of lime which is largely used. By dispensing with the preliminary boiling operation the time required for carrying out the bleaching process and the work and the steam required therefor are materially reduced, so that the reduction of the cost of the bleaching process is considerable,-

the cost of the ingredients being immaterial. The process is particularly advantageous in such cases where by preliminary boiling the material has been stained or otherwise injured. Therefore it is particularly useful in bleaching dyed goods. 5

In amodification of the process I subject the fiber material to a short preliminary treatment by means of diluted cold solutions of caustic alkalis or alkali metal carbonates having an addition of the above mentioned sulphonic-compounds for improving the wetting and permeating property thereof, whereupon the material is washed, neutralized and bleached, preferably by means of a bleach ing medium having my improved moistening media added thereto. I have found that thereby a beautiful bleaching effect is produced even when treating fiber material containing particles of shell, pectin substances and the like.

In the art of dyeing the aliphatically substituted aromatic sulpho acids or the salts thereof are distinguished from the known subsidiary ingredients used in dyeing, in that they may be universally used and that they have the aforesaid technical advantages. The acids as well as the salts thereof with the alkali metals, the alkali earth metals,

aluminum, chromium, copper and the like, are soluble in water; the solutions have a strong capillary activity and reduce the surface tension of the bath relatively to the dye-stuff and the fiber material. By reason of the property of the said sulpho-acids to produce soluble compounds with the said mordant metals, the inorganic mordants such as potassium-bichromate, chromium-fluoride,

alum, copper-sulphate, iron-sulphate, chloride of tin, etc, may be completely or in part substituted in mordant dyeing by the The moistcning and permeating action of i the said sulpho-acids and their salts can be further improved by adding thereto alcohols of one and higher valencies and soluble in water, such as methyl-alcohol, ethyl-alcohol, isopropyl-alcohol, mayl-alcohol, glycol-glycerine.

Further, the said sulphonic-acids may be added to the aforesaid bath heretofore used preparatory to bleaching.

Example 1, bleaching of piece go0tls.-100 kilogrammes of nettle fabric are bleached from 3 to 4 hours in a bleaching jigger by means of 500 liters of a chloride of lime bleaching'liquor of 0.7 B. (1 Twaddell) containing 0.4 gramme of sodium salt of isobutyl naphthalene sulphonic acid per liter, whereupon it is further treated in the usual way.

Example 2, dyeing 100 kilogrammes 0 f cotton g am.-Five kilogrammes of powdered indigo and kilogramme of potassium salt of cyclo-hexyl-naphthalene sulphonic acid are formed with three liters of water into a homogeneous paste, and the said paste is brought into a bath of about 3000 liters of water, 2.5 liters of soda solution of 30 B. (52.13 Twaddell and 1.8 kilogrammes of anhydrous sodium-hydro-sulfite at a'temperature of 40 C. (104 F.). Thereafter dyeing is carried on in the usual way.

Example 3, dyeing of 100 kilogram/mes of wool felt (hat felt).-1 kilogram of a suitable acid dye-stuif is formed into a paste with a solution of 0.8 kilogramme of isopropyl-naphthalene-sulphonic-acid and two liters of water, which paste is gradually added to the dyers bath of about 3000 liters together with two kilogrammes of concentrated sulphuric acid and 8 kilogrammes of calcined Glauber salt. The felt material is dyed in the usual way at boiling temperature to extraction of the bath.

By raw fibrous material is meant a material which contains the natural constituents of the fiber such as starches, gums, pectins and the like, and also contains contaminating material such as machine oil, grease and the like.

I claim: I

1. The process of bleaching raw fibrous material which comprises introducing the raw fibrous material into a cold bleaching liquor containing a salt of an aliphatically substituted aromatic sulphonic acid and an unstable chlorine compound and then completing the bleaching process in known manner.

2. The process of bleaching raw fibrous material which comprises introducing the raw fibrous material into a cold bath containing an alkali metal compound yielding hydroxyl ions in aqueous solution and then introducing the fibrous material into a cold bleaching liquor containing a salt of an aliphatically substituted aromatic sulphonic acid and an unstable chlorine compound and then completing the bleaching process in known manner.

3. The process of bleaching raw fibrous material which comprises introducing the said raw fibrous material into a cold bleaching bath containing a salt of an aliphatical- 1y substituted aromatic sulphonic acid, a water soluble'alcohol and an unstable chlorine compound and then completing the bleaching process.

4; The process of bleaching raw fibrous material which comprises introducing the said raw fibrous material into a cold bath containing an alkali metal compound yield- I ing hydroxyl ions in aqueous solution and then introducing the fibrous material into a cold bleaching liquor containing a salt of an alkyl substituted naphthalene sulphonic acid and bleaching powder and completing the bleaching process in known manner.

In testimony whereof I hereunto afiix my signature.

KURT LINDNER. 

